CN107925090B - Electrode active material slurry and lithium secondary battery comprising the same - Google Patents
Electrode active material slurry and lithium secondary battery comprising the same Download PDFInfo
- Publication number
- CN107925090B CN107925090B CN201780002529.9A CN201780002529A CN107925090B CN 107925090 B CN107925090 B CN 107925090B CN 201780002529 A CN201780002529 A CN 201780002529A CN 107925090 B CN107925090 B CN 107925090B
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- active material
- electrode active
- cellulose
- material slurry
- based compound
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- 239000002002 slurry Substances 0.000 title claims abstract description 130
- 239000007772 electrode material Substances 0.000 title claims abstract description 83
- 229910052744 lithium Inorganic materials 0.000 title claims description 42
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 41
- 239000001913 cellulose Substances 0.000 claims abstract description 76
- 229920002678 cellulose Polymers 0.000 claims abstract description 74
- 150000001875 compounds Chemical class 0.000 claims abstract description 73
- 238000006467 substitution reaction Methods 0.000 claims abstract description 42
- 239000011230 binding agent Substances 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000006258 conductive agent Substances 0.000 claims description 36
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 35
- 239000007773 negative electrode material Substances 0.000 claims description 35
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 33
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 33
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
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- 239000003610 charcoal Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 2
- 239000004020 conductor Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 39
- 239000006183 anode active material Substances 0.000 description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 20
- 239000007787 solid Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 239000002245 particle Substances 0.000 description 15
- 239000011149 active material Substances 0.000 description 13
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
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- 239000010936 titanium Substances 0.000 description 6
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical class [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
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- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 229910003936 Li(Ni0.5Mn0.3Co0.2)O2 Inorganic materials 0.000 description 2
- 229910004427 Li(Ni0.7Mn0.15Co0.15)O2 Inorganic materials 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
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- 229920002472 Starch Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical class O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 239000006231 channel black Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical class [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
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- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000006233 lamp black Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical class [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 239000006234 thermal black Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Chemical class 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229910000925 Cd alloy Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229910016848 F2SO2 Inorganic materials 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910013733 LiCo Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910017287 MnYO2 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910004027 NizO4 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- VIEVWNYBKMKQIH-UHFFFAOYSA-N [Co]=O.[Mn].[Li] Chemical class [Co]=O.[Mn].[Li] VIEVWNYBKMKQIH-UHFFFAOYSA-N 0.000 description 1
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- IDSMHEZTLOUMLM-UHFFFAOYSA-N [Li].[O].[Co] Chemical class [Li].[O].[Co] IDSMHEZTLOUMLM-UHFFFAOYSA-N 0.000 description 1
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- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical class [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 235000019325 ethyl cellulose Nutrition 0.000 description 1
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
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- 230000005484 gravity Effects 0.000 description 1
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- PTVWPYVOOKLBCG-ZDUSSCGKSA-N levodropropizine Chemical compound C1CN(C[C@H](O)CO)CCN1C1=CC=CC=C1 PTVWPYVOOKLBCG-ZDUSSCGKSA-N 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to an electrode active material slurry comprising: a) an electrode active material; b) a conductive material; c) a binder; d) a solvent; and e) a cellulose-based compound having a weight average molecular weight (Mw) of 2,000,000-3,000,000, a degree of substitution of 1.0 to 1.2, and a viscosity (Brookfield viscometer, speed 12rpm) of 4,000-10,000 cps. Since the cellulose-based compound having a specific range of molecular weight and substitution degree is used, the phase stability of the electrode active material slurry may be improved and the battery characteristics may be improved.
Description
Technical Field
Cross Reference to Related Applications
This application claims the benefit of korean patent application No. 10-2016-.
Technical Field
The present invention relates to an electrode active material slurry comprising a cellulose-based compound having a high molecular weight and a high degree of substitution, and an electrode and a lithium secondary battery comprising the same.
Background
In recent years, with the rapid development of the electronic industry and the communication industry, such as various information communication technologies (including mobile communications) and the like, portable electronic products and communication terminals, such as notebook computers, netbooks, tablet computers, mobile phones, smart phones, Personal Digital Assistants (PDAs), digital cameras, and camcorders, have been widely used to meet the demand for lightweight electronic devices, and thus there is an increasing interest in the development of secondary batteries as power sources for these devices.
The lithium secondary battery generally includes: a positive electrode in which a positive electrode active material layer is formed on at least one surface of a positive electrode current collector; an anode in which an anode active material layer is formed on at least one surface of an anode current collector; and a separator disposed between the positive electrode and the negative electrode to electrically insulate them.
The negative electrode may be formed by directly coating a negative electrode active material slurry in which negative electrode active material particles and a binder are dispersed in a solvent on a current collector and drying the coated current collector, or may be formed by coating a negative electrode active material slurry on a separate support, drying the coated support, and laminating a film peeled off from the support on the current collector.
Since the binder plays a role in maintaining the adhesion between the anode active material particles and the current collector and the adhesion between the anode active material particles during the preparation of the anode, the binder has a great influence on the performance of the electrode. Styrene-butadiene rubber (SBR) which is electrochemically stable and has an excellent effect even if it is used in a smaller amount than polyvinylidene fluoride (PVDF) is used as a binder, and in addition, a thickener is used to adjust the viscosity of the anode active material slurry.
Cellulose-based thickeners are mainly used as thickeners.
However, for low molecular weight cellulosic thickeners, there is a limitation that causes phase separation of the slurry. In addition, in the case of containing an excessive amount of the cellulose-based thickener, not only is it not easy to use the cellulose-based thickener in this process due to the increase in viscosity of the slurry, but also the amount of the electrode active material is reduced due to the increase in the weight ratio of the thickener to the active material, and thus the capacity of the battery is reduced.
Documents of the prior art
Korean patent application laid-open No. 10-2015-
Korean patent application laid-open No. 10-2014-0095804
Disclosure of Invention
Technical problem
One aspect of the present invention provides an electrode active material slurry having improved phase stability.
Another aspect of the present invention provides an electrode having improved adhesiveness by using an electrode active material slurry.
Another aspect of the present invention provides a lithium secondary battery having improved capacity and rate characteristics by including the electrode.
Technical scheme
According to an aspect of the present invention, there is provided an electrode active material slurry including:
(a) an electrode active material;
(b) a conductive agent;
(c) a binder;
(d) a solvent; and
(e) a cellulose-based compound having a weight average molecular weight (Mw) of 2,000,000 to 3,000,000, a degree of substitution of 1.0 to 1.2 and a viscosity (Brookfield viscometer, speed 12rpm) of 4,000cps to 10,000 cps.
Specifically, the weight average molecular weight (Mw) of the cellulose-based compound may be in the range of 2,500,000-3,000,000.
The cellulose-based compound may comprise carboxymethyl cellulose (CMC) or carboxyethyl cellulose.
The cellulose-based compound may be contained in an amount of 0.5 to 2.0 wt%, for example, 0.8 to 1.2 wt%, based on the total weight of the electrode active material slurry.
The electrode active material may include an anode active material, and the anode active material may include a single material selected from the group consisting of crystalline carbon, amorphous carbon, and a carbon composite, or a mixture of two or more thereof.
The weight ratio of the cellulose-based compound to the conductive agent may be in the range of 1:0.5 to 1: 2.
The binder may be contained in an amount of 0.5 to 3 wt% based on the total weight of the electrode active material.
The solvent may comprise water or an organic solvent.
According to another aspect of the present invention, there is provided an electrode comprising the electrode active material slurry.
The electrode may comprise a negative electrode.
According to another aspect of the present invention, there is provided a lithium secondary battery comprising an anode, a cathode, a separator provided between the anode and the cathode, and an electrolyte solution, wherein the anode in this case comprises the anode of the present invention.
Advantageous effects
According to the present invention, it is possible to prepare an electrode active material slurry having improved phase stability by using a cellulose-based compound having a specific range of molecular weight, substitution degree, and viscosity as a thickener, and to prepare a lithium secondary battery having improved battery capacity and rate performance using the same.
Detailed Description
Hereinafter, the present invention will be described in more detail in order to more clearly understand the present invention.
It should be understood that the words or terms used in the specification and claims should not be construed as meaning defined in commonly used dictionaries. It should be further understood that the terms or terms should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the technical spirit of the present invention, based on the principle that the inventor can best explain the present invention by appropriately defining the meaning of the terms or terms.
Specifically, in one embodiment of the present invention, there is provided an electrode active material slurry comprising:
(a) an electrode active material;
(b) a conductive agent;
(c) a binder;
(d) a solvent; and
(e) a cellulose-based compound having a weight average molecular weight (Mw) of 2,000,000 to 3,000,000, a degree of substitution of 1.0 to 1.2 and a 1% solution viscosity (Brookfield viscometer, speed 12rpm) of 4,000cps to 10,000 cps.
In the case where a cellulose-based compound used as a conventional thickener is used together with a binder and a conductive agent, it is difficult to adjust or maintain the viscosity of an electrode active material slurry over time due to uneven dispersion caused by a difference in specific gravity with the electrode active material. In the case where the amount of the solvent is increased to solve such a limitation, the capacity and rate performance of the secondary battery may be degraded due to a relative decrease in the solid content.
In particular, in the case where a cellulose-based compound is used together with the conductive agent, the cellulose-based compound affects the dispersibility of the conductive agent. For example, a cellulose-based compound having a low molecular weight is used together with a conductive agent, and since the conductive agent is agglomerated due to a low diffusion effect of the conductive agent, it is not uniformly mixed with an active material, and thus uniform dispersibility of the active material and the conductive agent on an electrode surface may not be expected.
In the present invention, the phase separation phenomenon of the electrode active material slurry may be improved by using a cellulose-based compound having a molecular weight, a substitution degree, and a viscosity within specific ranges as a thickener, and furthermore, the phase stability of the electrode active material slurry may be improved by reducing the number of particles of the cellulose-based compound remaining undissolved in water. Thus, a lithium secondary battery having improved battery capacity and rate performance can be prepared.
In the electrode active material slurry according to an embodiment of the present invention, the cellulose-based compound as the water-soluble polymer additive may include carboxyethyl cellulose or carboxymethyl cellulose (CMC) represented by the following formula 1, and may specifically include carboxymethyl cellulose.
[ formula 1]
In the formula 1, the first and second groups,
R1、R2and R3Each independently is a hydrogen atom or-CH2COOH, and
n is an integer of 100 to 3,000.
In addition, the cellulose-based compound may be used by adding a single material selected from the group consisting of methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, benzyl cellulose, and cellulose ether, or a mixture of two or more thereof, in addition to carboxymethyl cellulose or carboxyethyl cellulose.
According to one embodiment of the present invention, the weight average molecular weight (Mw) of the cellulose-based compound may be in the range of 2,000,000 to 3,000,000, for example 2,500,000 to 3,000,000.
The weight average molecular weight (Mw) of the cellulose-based compound can be measured by Gel Permeation Chromatography (GPC) with reference to polyacrylic acid (PAA) standards.
The molecular weight of the cellulose-based compound determines the length of the polymer chain, wherein if the weight average molecular weight of the cellulose-based compound is less than 2,000,000, phase separation of the electrode active material slurry, for example, sedimentation of the electrode active material as a solid component, may occur due to excessively low viscosity. In the case where the amount of the cellulose-based compound is increased in order to prevent this, the capacity of the secondary battery may be reduced because the amount of the electrode active material is reduced. In addition, if the weight average molecular weight of the cellulose-based compound exceeds 3,000,000, the solubility of the cellulose-based compound in the electrode active material slurry is reduced due to the increase in viscosity. In addition, since the viscosity of the electrode active material slurry increases, it is not easy to use a cellulose-based compound in this process. In the case of increasing the use of a solvent to solve such a limitation, the capacity and rate performance of the secondary battery may be reduced due to a relative decrease in the solid content.
In addition, the Degree of Substitution (DS) of the cellulose-based compound may be in the range of 1.0 to 1.2.
The expression "degree of substitution" denotes the carboxymethyl group (-CH) in each repeating unit of cellulose in place of the hydroxyl group of the cellulose2COOH), wherein the solubility of the cellulosic compound in water may vary depending on the degree of substitution. The degree of substitution of cellulosic compounds can be estimated by measuring the relative amount of COOH present in the sample using a Nuclear Magnetic Resonance (NMR) spectrometer.
In general, when the degree of substitution of a cellulose-based compound is high, the solubility in water increases, and when the degree of substitution is low, the solubility in water decreases. The solubility of the cellulose-based compound in water may ultimately affect the dispersion properties of the electrode active material slurry, wherein the dispersibility of the electrode active material slurry may be improved as the solubility in water becomes higher. In addition, if the dispersibility of the electrode active material slurry is improved, the slurry coating effect may be improved, and thus the productivity may be improved.
In the present invention, since the dispersibility of the active material and the conductive agent can be improved by containing the cellulose-based compound having a degree of substitution of 1.0 or more, for example, 1.0 to 1.2, the number of particles (the number of microgels) of the cellulose-based compound remaining undissolved in water can be reduced. Therefore, for an electrode prepared using the electrode active material slurry having improved dispersibility, a smooth current can be formed inside thereof.
In the case where the degree of substitution of the cellulose-based compound is less than 1.0, the microgel count may increase due to a decrease in solubility in water. In addition, the cellulose-based compound plays a role of providing electrostatic repulsion by combining with the active material and the conductive agent in the electrode active material slurry, wherein in the case where the degree of substitution of the cellulose-based compound is less than 1.0, since the reaction is weak and the dispersibility of the active material and the conductive agent is reduced, the battery performance may be reduced. As the degree of substitution of the cellulose-based compound becomes higher, the solubility in water increases, but it is technically difficult to control the degree of substitution to 1.2 or more.
The number of visually detectable and discernible particles of the cellulose-based compound that are not dissolved in water (the number of microgels) in the electrode active material slurry can be controlled depending on the degree of substitution with the cellulose-based compound. In particular, the microgel count may desirably be below 20, for example in the range of 5 to 20, per 0.25ml of electrode active material slurry. In the case where the microgel number is more than 20, the dispersibility of the active material and the conductive agent may be reduced, thereby increasing the resistance of the battery, and defects may occur on the surface of the electrode due to weak cohesion.
The viscosity of the cellulose-based compound can be controlled according to the molecular weight of the cellulose-based compound, and specifically, the viscosity of the cellulose-based compound is proportional to the molecular weight.
The viscosity of a 1% solution of the cellulosic compound may be in the range of about 4,000cps to about 10,000 cps.
The viscosity of a 1% aqueous solution of a cellulose-based compound can be measured at room temperature using a Brookfield viscometer (model: LVDV2T) with spindle No. 4 at a speed of 12 rpm.
In the case where the 1% solution viscosity of the cellulose-based compound is less than 4,000cps, it may be difficult to perform a uniform coating process since phase separation occurs between the active material and the solvent when preparing the slurry. For example, a cellulose-based compound having a weight average molecular weight of 1,200,000, a degree of substitution of 1.2, and a viscosity of 2,200cps has a high degree of substitution and thus has a high solubility in water, resulting in a small number of microgels, but has a low viscosity of 2,200cps, resulting in phase separation of slurry, thereby lowering the stability of the slurry. In the case where a large amount of a cellulose-based compound is added in order to ensure processability, if the solid content is reduced, the energy density of the battery may be reduced or the battery capacity may be reduced.
In contrast, in the case where the viscosity of the cellulose-based compound is greater than 10,000cps, the cellulose-based compound is insoluble in the electrode active material slurry due to the increase in viscosity, and thus it may not be feasible to use the cellulose-based compound in this process.
In the electrode active material slurry according to an embodiment of the present invention, the content of the cellulose-based compound may be 0.5 to 2 wt%, for example, 0.8 to 1.2 wt%, based on the total weight of solid matters in the electrode active material slurry.
If the amount of the cellulose-based compound is less than 0.5 wt%, phase stability of the electrode active material slurry, for example, electrode active material slurry flow-down, may not be ensured since the effect due to the use of the thickener during the coating of the electrode active material slurry is insignificant. Therefore, in the case where the phase stability of the electrode active material slurry is not ensured, the coating of the electrode active material slurry is not easy, and the binder may be unevenly distributed on the surface of the electrode during the drying process. In this case, since adhesion between the active material particles and the current collector is not ensured, there is a possibility that a peeling phenomenon of the electrode occurs.
In contrast, in the case where the amount of the cellulose-based compound exceeds 2 wt%, it may be difficult to ensure high capacity of the battery not only because the viscosity of the electrode active material slurry increases, making the application of the electrode active material slurry difficult, but also because the amount of the electrode active material in the slurry decreases.
In the case where a low molecular weight cellulose-based compound is used together with a conductive agent during the preparation of a conventional electrode active material slurry, uniform mixing with an active material may not be achieved due to agglomeration of the conductive agent resulting from a decrease in the diffusion effect of the conductive agent. As a result, since the phase stability of an electrode active material slurry in which a cellulose-based compound having a low molecular weight and/or a low degree of substitution is used may not be expected, the capacity and rate performance are reduced.
In the present invention, since an electrode active material slurry containing a cellulose-based compound having a high molecular weight and a substitution degree in a specific range is provided, the problems in the related art can be solved. That is, since the cellulose-based compound having a molecular weight and a substitution degree within a specific range has high water solubility and excellent dispersibility as compared to other cellulose-based compounds having a low molecular weight and/or a low substitution degree, the effect of reducing the thickening and solid settling rate of the electrode active material slurry of the present invention can be achieved. Accordingly, since the adhesion of the electrode active material is improved to prevent the electrode active material from being peeled off from the current collector, excellent battery performance can be achieved.
In addition, the resistance characteristics of the battery affect the output performance of the lithium secondary battery. The resistance characteristics are significantly affected by the dispersion state of the components in the electrode active material slurry. For example, in the case where the electrode active material, the conductive agent, and the binder are not present in a uniformly dispersed state but are agglomerated together, since a channel through which current can flow in the electrode is not locally formed, the resistance in the battery may increase or a current concentration phenomenon may occur, and thus, the performance and stability of the battery may be degraded.
In the present invention, since the electrode active material slurry including the cellulose-based compound having the molecular weight and the substitution degree within the specific ranges is provided, the dispersibility of the electrode active material slurry is improved, and thus the battery characteristics can be improved.
In the electrode active material slurry according to an embodiment of the present invention, the electrode active material (a) may include a negative electrode active material.
As the negative electrode active material, one kind of carbon-based negative electrode active material such as crystalline carbon, amorphous carbon, or carbon composite, or a combination of two or more kinds thereof may be used, and the negative electrode active material may be crystalline carbon, for example, graphitic carbon such as natural graphite and artificial graphite.
The content of the negative electrode active material may be 60 wt% to 97 wt%, for example, 80 wt% to 97 wt%, based on the total weight of solids in the electrode active material slurry.
In addition, in the electrode active material slurry of the present invention, the conductive agent (b) is not particularly limited as long as it has conductivity without causing side reactions with other elements of the secondary battery, and for example, a single material selected from the group consisting of: natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, carbon nanotubes, fullerenes, carbon fibers, metal fibers, fluorocarbons, aluminum, nickel powder, zinc oxide, potassium titanate, titanium oxide, and polyphenylene derivatives.
The conductive agent may be added in an amount of about 0.05 wt% to about 3 wt%, based on the total weight of solids in the electrode active material slurry, and the weight ratio of the cellulose-based compound to the conductive agent may be in the range of 1:0.5 to 1:2, for example, 1:0.5 to 1: 1.5. In the case where the weight ratio of the cellulose-based compound to the conductive agent is outside the above range, an agglomeration phenomenon of the electrode slurry may occur due to uneven dispersion of the conductive agent, and it may be difficult to prepare a uniform electrode if the particles are not uniformly dispersed. In addition, since the electrochemical distribution is not uniform, the resistance in the electrode may increase or a current concentration phenomenon may occur, and thus the performance and stability of the battery may be degraded.
Further, in the electrode active material slurry of the present invention, the binder (c) is used for holding the shaped article by binding the active material particles, wherein the binder may comprise a single material selected from the group consisting of: acrylonitrile-butadiene rubber, styrene-butadiene rubber (SBR), hydroxyethylcellulose, polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride (PVDF), polyvinyl alcohol, starch, polyacrylonitrile, hydroxypropylcellulose, regenerated cellulose, polymethyl methacrylate, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylate, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, and Polytetrafluoroethylene (PTFE).
In this case, since the rubbery binder selected from the group consisting of acrylonitrile-butadiene rubber, styrene-butadiene rubber (SBR), and acrylic rubber, and the polymer resin such as polyvinylidene fluoride may be economical and environmentally friendly, may not cause a hazard to the health of workers, and may have a greater binding effect than a non-aqueous binder, the ratio of active materials for the same volume may be increased. Therefore, the capacity of the battery can be increased.
The binder may be included in an amount of about 0.5 wt% to about 3 wt% based on the total weight of solids in the electrode active material slurry. In the case where the amount of the binder is less than 0.5 wt%, electrode adhesiveness may not be ensured, and in the case where the amount of the binder is more than 3 wt%, electrode resistance may increase.
The solvent (d) may include water or an organic solvent, such as N-methylpyrrolidone (NMP) and alcohol, and may be used in an amount such that the solvent has an appropriate viscosity to dissolve and disperse the electrode active material, the binder, and the conductive agent, in consideration of the coating thickness and the manufacturing yield of the electrode active material slurry. For example, the solvent may be included so that the concentration of the solid matter in the electrode active material slurry including the negative electrode active material, the binder, the conductive agent, and the cellulose-based compound is in the range of 50 wt% to 95 wt%, for example, 70 wt% to 90 wt%.
In addition, in one embodiment of the present invention, an electrode including the electrode active material slurry may be provided, and in particular, the electrode may include a negative electrode.
The anode current collector is coated with the anode active material slurry, and then the anode may be prepared by drying and rolling the coated anode current collector.
The anode current collector is generally prepared to a thickness of 3 μm to 500 μm. The anode current collector is not particularly limited as long as it has conductivity without causing undesirable chemical changes in the battery, and for example, copper, stainless steel, aluminum, nickel, titanium, fired carbon, copper or stainless steel surface-treated with one of carbon, nickel, titanium or silver, or an aluminum-cadmium alloy may be used. In addition, similar to the cathode current collector, minute irregularities may be formed on the surface of the current collector in order to improve the adhesion of the anode active material, and the anode current collector may be used in various shapes such as a film, a sheet, a foil, a net, a porous body, a foam, or a nonwoven fabric body.
In addition, in one embodiment of the present invention, there is provided a lithium secondary battery comprising the electrode of the present invention.
Specifically, in one embodiment of the present invention, there is provided a lithium secondary battery including: a negative electrode, a positive electrode, a separator provided between the negative electrode and the positive electrode, and an electrolyte solution, wherein the negative electrode comprises the negative electrode of the present invention.
The lithium secondary battery of the present invention may be prepared by typical methods known in the art. For example, the lithium secondary battery may be prepared by disposing a porous separator between a positive electrode and a negative electrode and injecting a nonaqueous electrolyte solution.
In this case, the positive electrode may be prepared by: a positive electrode active material slurry in which a positive electrode active material and optionally a conductive agent and a binder are mixed with a predetermined solvent is applied to a positive electrode current collector, and then the applied positive electrode current collector is dried and roll-pressed.
The positive electrode current collector is generally prepared to a thickness of 3 μm to 500 μm. The positive electrode current collector is not particularly limited as long as it has conductivity without causing undesirable chemical changes in the battery, and for example, stainless steel, aluminum, nickel, titanium, fired carbon, or aluminum or stainless steel surface-treated with one of carbon, nickel, titanium, silver, and the like may be used.
Minute irregularities may be formed on the surface of the cathode current collector in order to improve the adhesion of the cathode active material, and the cathode current collector may have various shapes such as a film, a sheet, a foil, a mesh, a porous body, a foam, and a non-woven body.
The positive electrode active material is a compound capable of reversibly intercalating and deintercalating lithium, wherein the positive electrode active material may specifically include a lithium composite metal oxide containing lithium and at least one metal such as cobalt, manganese, nickel or aluminum. Specifically, the lithium composite metal oxide may include a lithium manganese-based oxide (e.g., LiMnO)2、LiMn2O4Etc.), lithium cobalt oxides (e.g., LiCoO)2Etc.), lithium nickel-based oxides (e.g., LiNiO)2Etc.), lithium nickel manganese based oxidationObject (e.g., LiNi)1-YMnYO2(wherein 0)<Y<1)，LiMn2- ZNizO4(wherein 0)<Z<2) Etc.), lithium nickel cobalt-based oxides (e.g., LiNi)1-Y1CoY1O2(wherein 0)<Y1<1) Lithium manganese cobalt oxides (e.g., LiCo)1-Y2MnY2O2(wherein 0)<Y2<1)，LiMn2-Z1Coz1O4(wherein 0)<Z1<2) Etc.), lithium nickel manganese cobalt oxides (e.g., Li (Ni)pCoqMnr1)O2(wherein 0)<p<1，0<q<1，0<r1<1, and p + q + r1 ═ 1) or Li (Ni)p1Coq1Mnr2)O4(wherein 0)<p1<2，0<q1<2，0<r2<2, and p1+ q1+ r2 ═ 2), or a lithium nickel cobalt transition metal (M) oxide (e.g., Li (Ni)p2Coq2Mnr3MS2)O2(wherein M is selected from the group consisting of aluminum (Al), iron (Fe), vanadium (V), chromium (Cr), titanium (Ti), tantalum (Ta), magnesium (Mg), and molybdenum (Mo), p2, q2, r3, and s2 are atomic fractions of each individual element, where 0 is<p2<1，0<q2<1，0<r3<1，0<S2<1, and p2+ q2+ r3+ S2 ═ 1), etc.), and may contain any one of them or a mixture of two or more of them. Among these materials, the lithium composite metal oxide may include LiCoO in terms of improving capacity characteristics and stability of a battery2，LiMnO2，LiNiO2Lithium nickel manganese cobalt oxide (e.g., Li (Ni))0.6Mn0.2Co0.2)O2、Li(Ni0.5Mn0.3Co0.2)O2、Li(Ni0.7Mn0.15Co0.15)O2Or Li (Ni)0.8Mn0.1Co0.1)O2) Or lithium nickel cobalt aluminum oxides (e.g., LiNi)0.8Co0.15Al0.05O2Etc.). In view of significant improvement due to control of the type and content ratio of elements constituting the lithium composite metal oxide, the lithium composite metal oxide may contain Li (Ni)0.6Mn0.2Co0.2)O2、Li(Ni0.5Mn0.3Co0.2)O2、Li(Ni0.7Mn0.15Co0.15)O2Or Li (Ni)0.8Mn0.1Co0.1)O2Any one of them or a mixture of two or more of them may be used.
The content of the positive electrode active material may be 80 to 99% by weight, based on the total weight of solids in the positive electrode active material slurry.
The conductive agent is generally added in an amount of 1 to 30% by weight, based on the total weight of solids in the positive electrode active material slurry.
Any conductive agent may be used without particular limitation so long as it has suitable conductivity without causing undesirable chemical changes in the battery, for example, a conductive material such as graphite; carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; conductive fibers such as carbon fibers or metal fibers; metal powders such as fluorocarbon powders, aluminum powders, and nickel powders; conductive whiskers such as zinc oxide whiskers and potassium titanate whiskers; conductive metal oxides such as titanium oxide; or a polyphenylene derivative. Specific examples of the commercial conductive agent may include acetylene black-based products (Chevron Chemical Company), dan black (Denka black) (danka Singapore Private Company Limited (Denka Singapore Private price Limited)), or Gulf Oil Company (Gulf Oil Company)), ketjen black, Ethylene Carbonate (EC) -based products (emmak Company), Vulcan XC-72 (Cabot Company), and Super P (Timcal Graphite & Carbon).
The binder is a component that contributes to adhesion between the active material and the conductive agent and adhesion to the current collector, wherein the binder is generally added in an amount of 1 to 30 wt% based on the total weight of solids in the positive electrode active material slurry. Examples of the binder may be polyvinylidene fluoride, polyvinyl alcohol, starch, regenerated cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluororubber, and various copolymers.
The solvent may include an organic solvent, such as N-methyl-2-pyrrolidone (NMP), and may be used in an amount such that a desired viscosity is obtained when a cathode active material and, optionally, a binder and a conductive agent are included. For example, the solvent may be included such that the concentration of solids in the positive electrode active material slurry is in the range of 50 wt% to 95 wt%, for example, 70 wt% to 90 wt%.
In addition, the separator may include a porous polymer film, for example, a porous polymer film prepared from a single one of polyolefin-based polymers such as an ethylene homopolymer, a propylene homopolymer, an ethylene/butadiene copolymer, an ethylene/hexene copolymer, and an ethylene/methacrylate copolymer, or a laminate of two or more thereof. In addition, a typical porous nonwoven fabric, such as a nonwoven fabric formed of high-melting glass fibers or polyethylene terephthalate fibers, may be used, but the present invention is not limited thereto.
The lithium salt that may be contained in the non-aqueous electrolyte used in the present invention may be used without limitation as long as it is generally used for an electrolyte solution for a lithium secondary battery. For example, any one selected from the group consisting of: f-、Cl-、Br-、I-、NO3 -、N(CN)2 -、BF4 -、ClO4 -、PF6 -、(CF3)2PF4 -、(CF3)3PF3 -、(CF3)4PF2 -、(CF3)5PF-、(CF3)6P-、CF3SO3 -、CF3CF2SO3-、(CF3SO2)2N-、(F2SO2)2N-、CF3CF2(CF3)2CO-、(CF3SO2)2CH-、CF3(CF2)7SO3 -、CF3CO2 -、CH3CO2 -、SCN-And (CF)3CF2SO2)2N-。
In addition, the lithium secondary battery according to the embodiment of the present invention may include all types of typical lithium secondary batteries, such as a lithium metal secondary battery, a lithium ion secondary battery, a lithium polymer secondary battery, or a lithium ion polymer secondary battery.
The shape of the lithium secondary battery of the present invention is not particularly limited, and a cylindrical type (using a can), a prismatic type, a pouch type, or a coin type may be used.
The lithium secondary battery of the present invention can be used as a power source for various electronic products. For example, the lithium secondary battery of the present invention may be used for portable phones, mobile phones, game consoles, portable televisions, notebook computers, and calculators, but the present invention is not limited thereto.
Hereinafter, the present invention will be described in detail according to specific embodiments. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these exemplary embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Examples
I. Preparation of solutions of cellulose-based compounds
Preparation examples 1 to 6 and comparative examples 1 to 3
1g of carboxymethyl cellulose (manufactured by Nippon paper-making chemical Co., Ltd.) having a molecular weight and a degree of substitution shown in Table 1 below was dissolved in 99g of water to prepare a 1% solution of carboxymethyl cellulose.
The viscosity of the 1% solution of the prepared carboxymethyl cellulose and the number of particles (microgels) of the cellulose-based compound remaining in the solution without being dissolved in water were measured, and the results are shown in table 1 below. In this case, the viscosity was measured using a Brookfield viscometer (model: LVDV2T) spindle 4 at a shear rate of 12rpm and 25 ℃.
[ Table 1]
As confirmed in table 1, for preparation examples 1 to 6 containing carboxymethylcellulose having a weight average molecular weight of 2,000,000 to 3,000,000, a degree of substitution of 1.0 to 1.2, and an average 1% solution viscosity of about 4,000cps to 10,000cps, it was found that the number of microgels was small, about 20 or less.
In contrast, for the solutions containing carboxymethyl cellulose having a low degree of substitution of 0.8 as in comparative examples 1 and 2, it was found that the microgel count in the solutions was large, 70 and 200, respectively, due to the decrease in solubility.
For the solution containing carboxymethylcellulose having a weight average molecular weight of 1,200,000 and a degree of substitution of 1.2 as in comparative example 3, it was confirmed that the microgel count was small due to the high degree of substitution, but the 1% solution viscosity was low, 2,200cps, due to the low molecular weight.
Preparation of negative active Material slurry
Example 1.
A negative electrode active material in which spherical artificial graphite and flake natural graphite were mixed in a weight ratio of 9:1, graphite as a conductive agent, styrene-butadiene rubber (SBR) as a binder, and carboxymethyl cellulose (having a molecular weight of 2,000,000, a degree of substitution of 1.2, and a 1% solution viscosity of 4,000cps) used in preparation example 1 were mixed in a weight ratio of 96.5:1.5:0.8:1.2 by adding water (H) thereto2O) so that the concentration of the solid matter in the slurry was 85 wt%, to prepare a negative electrode active material slurry.
Example 2.
A negative electrode active material slurry was prepared in the same manner as in example 1, except that the ratio of the binder to the carboxymethyl cellulose in example 1 was changed to 1.2: 0.8.
Example 3.
A negative electrode active material slurry was prepared in the same manner as in example 1, except that carboxymethyl cellulose (molecular weight of 3,000,000, degree of substitution of 1.0, 1% solution viscosity of 10,000cps) used in preparation example 4 was used instead of the carboxymethyl cellulose compound used in example 1.
Example 4.
A negative electrode active material slurry was prepared in the same manner as in example 3, except that the ratio of the binder to the carboxymethyl cellulose in example 3 was changed to 1.2: 0.8.
Example 5.
A negative electrode active material slurry was prepared in the same manner as in example 1, except that carboxymethyl cellulose (molecular weight 2,500,000, degree of substitution 1.2, 1% solution viscosity 6,000cps) used in preparation example 5 was used instead of carboxymethyl cellulose used in example 1.
Example 6.
A negative electrode active material slurry was prepared in the same manner as in example 1, except that carboxymethyl cellulose (molecular weight 2,800,000, degree of substitution 1.0, 1% solution viscosity 8000cps) used in preparation example 6 was used instead of carboxymethyl cellulose used in example 1.
Comparative example 4.
A negative electrode active material slurry was prepared in the same manner as in example 1, except that carboxymethyl cellulose (molecular weight 2,000,000, substitution degree 0.8, 1% solution viscosity 4,000cps) of comparative example 1 was used instead of carboxymethyl cellulose used in example 1.
Comparative example 5.
A negative electrode active material slurry was prepared in the same manner as in example 1, except that carboxymethyl cellulose (molecular weight of 3,000,000, degree of substitution of 0.8, 1% solution viscosity of 10,000cps) used in comparative example 2 was used instead of carboxymethyl cellulose used in example 1.
Comparative example 6.
A negative electrode active material slurry was prepared in the same manner as in example 1, except that carboxymethyl cellulose (molecular weight of 1,200,000, degree of substitution of 1.2, 1% solution viscosity of 2,200cps) used in comparative example 3 was used instead of carboxymethyl cellulose used in example 1.
Comparative example 7.
A negative electrode active material slurry was prepared in the same manner as in comparative example 6, except that the ratio of the negative electrode active material to the conductive agent to the binder to the carboxymethyl cellulose in comparative example 6 was changed to 94.5:1.8:1.5: 2.2.
Comparative example 8.
A negative electrode active material slurry was prepared in the same manner as in example 1, except that the ratio of the negative electrode active material to the conductive agent to the binder to the carboxymethyl cellulose in example 1 was changed to 94.5:1.8:1.5: 2.2.
Electrode and secondary battery preparation
Example 7.
(preparation of negative electrode)
After a copper (Cu) thin film as an anode current collector was coated with the anode active material slurry prepared in example 1 and dried, roll pressing was performed to prepare an anode having a thickness of 10 μm.
(Secondary Battery production)
A coin-type lithium secondary battery was prepared using Li metal as a counter electrode, a polyolefin separator was disposed between a negative electrode and the Li metal, and then an electrolyte in which 1M LiPF was injected6Dissolved in a solvent prepared by mixing Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 30: 70.
Example 8.
An anode and a coin-type lithium secondary battery including the same were prepared in the same manner as in example 7, except that the anode active material slurry prepared in example 2 was used instead of the anode active material slurry prepared in example 1.
Example 9.
An anode and a coin-type lithium secondary battery including the same were prepared in the same manner as in example 7, except that the anode active material slurry prepared in example 5 was used instead of the anode active material slurry prepared in example 1.
Example 10.
An anode and a coin-type lithium secondary battery including the same were prepared in the same manner as in example 7, except that the anode active material slurry prepared in example 6 was used instead of the anode active material slurry prepared in example 1.
Comparative example 9.
An anode and a coin-type lithium secondary battery including the same were prepared in the same manner as in example 7, except that the anode active material slurry prepared in comparative example 5 was used instead of the anode active material slurry prepared in example 1.
Comparative example 10.
An anode and a coin-type lithium secondary battery including the same were prepared in the same manner as in comparative example 9, except that the anode active material slurry prepared in comparative example 6 was used instead of the anode active material slurry prepared in comparative example 5.
Comparative example 11.
An anode and a coin-type lithium secondary battery including the same were prepared in the same manner as in comparative example 9, except that the anode active material slurry prepared in comparative example 7 was used instead of the anode active material slurry prepared in comparative example 5.
Comparative example 12.
An anode and a coin-type lithium secondary battery including the same were prepared in the same manner as in comparative example 9, except that the anode active material slurry prepared in comparative example 8 was used instead of the anode active material slurry prepared in comparative example 5.
Examples of the experiments
Experimental example 1: phase stability experiment of negative active material slurry
The average particle diameters of solids in the anode active material slurries prepared in examples 1 to 6 and the anode active material slurries prepared in comparative examples 4 to 8 were measured using a fine gauge (grind gauge, manufacturer: SHEEN/SB, range: 0-100 μm) method, and the results are listed in Table 2 below.
Next, 50g each of the negative electrode active material slurries of examples 1 to 6 and the negative electrode active material slurries of comparative examples 4 to 8 was placed in 11 bottles of 50ml, and the height of the bottom sedimentation amount (sedimentation rate (%)) was measured based on 100% height of the negative electrode active material slurry after 3 days. The results are shown in Table 2 below.
[ Table 2]
As confirmed in table 2, with respect to the negative electrode active material slurries of examples 1 to 6 of the present invention, it was found that the amount of sedimentation (sedimentation rate) based on 100% height of the negative electrode active material slurry after 3 days was in the range of 1.0% to 3.4%, and the average particle diameter of the solid matter in the slurry was small and 45 μm or less.
Particularly in the examination of the anode active material slurries of examples 1 to 4, even in the case of using carboxymethyl cellulose having the same molecular weight and substitution degree, it was found that the sedimentation rates (2.0% and 1.0%) of the anode active material slurries of examples 1 and 3 having a high carboxymethyl cellulose content ratio were lower, respectively, with respect to the sedimentation rates (3.4% and 1.5%) of the anode active material slurries of examples 2 and 4.
In contrast, with the anode active material slurries of comparative examples 4 and 5, which contained carboxymethylcellulose having a low degree of substitution of 0.8, it was found that the average particle diameters of the solid matters in the slurries were 60 μm and 73 μm, respectively, which were larger than those of the anode active material slurries of examples 1 to 6, due to the low solubility.
In addition, with respect to the anode active material slurry of comparative example 6, which contained carboxymethyl cellulose having a low weight average molecular weight of 1,200,000, it was found that the precipitation rate was increased because phase separation occurred in the anode active material slurry due to low viscosity.
With the anode active material slurries of comparative examples 7 and 8, which contained an excessive amount of carboxymethyl cellulose, the sedimentation rate was low, and the average particle diameter was not significantly different from that of the anode active materials of examples, but since the amount of the electrode active material was relatively reduced, it was found that, as described later, the overall performance such as capacity characteristics was reduced.
Experimental example 2: measurement of adhesion of negative electrode
The adhesion of the negative electrodes prepared in examples 7 to 10 and comparative examples 9 to 12 was measured, and the results are shown in table 3 below. In this case, the adhesiveness was measured according to the 180-degree peel method.
Experimental example 3: capacity and efficiency characteristic test of lithium secondary battery
The lithium secondary batteries prepared in examples 7 to 10 and the lithium secondary batteries prepared in comparative examples 9 to 12 were charged to a voltage of 0.005V at a Constant Current (CC) of 1.0C at room temperature, and then the first-cycle charge was performed by charging the batteries to a current of 0.005% of 1.0C at a Constant Voltage (CV) of 0.005V. After the lithium secondary battery was left to stand for 20 minutes, the battery was discharged to a voltage of 1.5V at constant currents of 0.2C and 1.0C to measure the discharge capacity of the first cycle. The results are shown in Table 3 below.
[ Table 3]
Referring to table 3, since the negative electrodes prepared in examples 7 to 10 of the present invention had high adhesion of 18gf/15mm or more and high discharge capacity of 98.9% or more on average, it can be found that the battery capacity was improved.
In contrast, with respect to the negative electrode of comparative example 9 using the negative electrode active material slurry of comparative example 5 in which the average particle diameter of the solid matter in the slurry was large, and the negative electrode of comparative example 10 using the negative electrode active material slurry of comparative example 6 in which the slurry settling rate was high, it was found that the adhesion of the negative electrode was low, 12gf/15mm or less, and the discharge capacity was relatively reduced compared to examples 7 to 10, because the phase stability of the slurry was lowered.
For the lithium secondary batteries of comparative examples 11 and 12 using the negative electrode active material including an excessive amount of carboxymethyl cellulose, it was found that the adhesion of the negative electrode was high, 26gf/15mm or more, due to the excessive amount of carboxymethyl cellulose, but the discharge capacity was relatively decreased compared to examples 7 to 10, due to the relative decrease in the amount of the electrode active material.
While particular embodiments of the present invention have been described above, various applications and modifications will become apparent to those skilled in the art without departing from the scope of the present invention.
Claims (12)
1. An electrode active material slurry comprising:
(a) an electrode active material;
(b) a conductive agent;
(c) a binder;
(d) a solvent; and
(e) a cellulose-based compound having a weight average molecular weight (Mw) of 2,000,000 to 3,000,000 and a degree of substitution of 1.0 to 1.2, and a viscosity of 4,000cps to 10,000cps as measured in a 1% aqueous solution of the cellulose-based compound using a Brookfield viscometer at a speed of 12rpm,
wherein the expression "degree of substitution" denotes the carboxymethyl-CH group in each cellulose repeating unit replacing the hydroxyl group of the cellulose2Average number of COOH.
2. The electrode active material slurry according to claim 1, wherein the cellulose-based compound comprises carboxymethyl cellulose or carboxyethyl cellulose.
3. The electrode active material slurry according to claim 1, wherein the cellulose-based compound has a weight average molecular weight (Mw) in the range of 2,500,000 to 3,000,000.
4. The electrode active material slurry according to claim 1, wherein the cellulose-based compound is contained in an amount of 0.5 to 2.0 wt% based on the total weight of the electrode active material slurry.
5. The electrode active material slurry according to claim 4, wherein the cellulose-based compound is contained in an amount of 0.8 to 1.2 wt% based on the total weight of the electrode active material slurry.
6. The electrode active material slurry according to claim 1, wherein the electrode active material is a negative electrode active material.
7. The electrode active material slurry of claim 6, wherein the negative active material comprises a single material selected from the group consisting of crystalline carbon, amorphous carbon, and a carbon composite, or a mixture of two or more thereof.
8. The electrode active material slurry according to claim 1, wherein the weight ratio of the cellulose-based compound to the conductive agent is in the range of 1:0.5 to 1: 2.
9. The electrode active material slurry according to claim 1, wherein the solvent comprises water or an organic solvent.
10. An electrode comprising the electrode active material slurry according to claim 1.
11. The electrode of claim 10, wherein the electrode is a negative electrode.
12. A lithium secondary battery comprising:
a negative electrode;
a positive electrode;
a separator disposed between the anode and the cathode; and
an electrolyte solution is added to the electrolyte solution,
wherein the anode comprises the anode of claim 11.
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| KR102158455B1 (en) * | 2019-02-20 | 2020-09-23 | 한국에너지기술연구원 | Method of manufacturing supercapacitor by 3d printing of electrode ink including dispersant |
| CN111312967B (en) * | 2020-02-27 | 2022-06-07 | 河北金力新能源科技股份有限公司 | Ceramic coating slurry and preparation method thereof, lithium battery diaphragm and lithium battery |
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| KR102253883B1 (en) | 2013-05-23 | 2021-05-18 | 제온 코포레이션 | Slurry composition for secondary-battery negative electrode, secondary-battery negative electrode, and secondary battery |
| KR20140140980A (en) | 2013-05-30 | 2014-12-10 | 주식회사 엘지화학 | Electrode for lithium secondary battery and lithium secondary battery comprising the same |
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